Metallizable triazine azo compounds



Patented Mar. 19, 1946 EJNH'E METALLIZABLE TRIAZINE AZO COMPOUNDS Basel, Switzerland No Drawing. Application July 11, 1941, Serial No. 402,023. in Switzerland July 19, 1940 9 Claims.

In U. S. Patent'No. 2,084,731, among other things, it is pointed out that valuable dyestuffs are obtained if the diazotized aminoazo dyestuffs obtained by the union of diazotized aminosalicylic acids and 1amino-2-methoxynaphthalene sulphonic acids are combined with the ternary condensation products which are themselves obtained by reaction of one molecule of a cyanuric halide, such as cyanuric chloride or cyanuric bromide, with one molecule of a 1-amino-8- hydroxynaphthalene sulphonic acid, one mole- 01113 of an aminoazo dyestufi of the type of 4- aminol'hydroxyazobenzene-B'-carboxylic acid and 1 molecule of a primary or secondary amine. The dyestuffs thus obtained can be remarkable for,' first1y, the purity of their dyed shades and, secondly, the good wet-fastness properties of their dyeings which have been developed with copper compounds.

It has now been found that new dyestuiis can be obtained, the dyeings of which, when developed with copper compounds, exhibit still better Wetfastness properties, if the above mentioned ter-' nary condensation products are combined with the diazotized mono-azo dyestuffs which are themselves obtained by coupling diazotized aminosalicylio acids with compounds of the general formula in which :n stands for hydrogen or alkoxy.

The same dyestuffs are also obtained if the diazotized monoazo dyestuff be first of all combined with the 1amino-B-hydroxynaphthalene sulphonic acid in alkaline medium and the reaction between the disazo dyestuff and the cyanurichalide, the aminoazo dyestuff and the primary or secondary amine be then carried out, it being permissible for the latter reactions to take place in any desired sequence.

Finally, it is also possible to prepare primary or secondary condensation products from the 1- amino 8 hydroxynaphthalene sulphonic acid,-

hydroxyazobenzene-S'-carboxylic acid, in addition to the product named, there come in question 4-amino 4'-hydroxyazobenzene 5'-methyl 3'- carboxylic acid, as well as other substitution products of these dyestuffs, such as 4-amino-3- chloro-, or -3-methoxy-, or -3-sulfo-4-hydroxyazobenzene-3'-carboxylic acid.

Among the diazotized aminosalicylic acids, the

which has been explained above, the most im-'- portant are m-toluidine and 1-amino-2-methoxyor -2ethoxy-5-methylbenzene.

Among the primary and secondary amines, both aliphatic and aromatic amines come into consideration, for example, monomethylor monoethylamine, monopropylamine, diethylamine, aniline, monomethylaniline, p-toluidine, p-naphthylamine, sulphonic and carboxylic acids of these compounds, aminoazo dyestuffs-among which aminoazo dyestuffs of the type of i-amino- 4'hydroxyazobenzene-3'-carboxylic acid are also includedand., finally, polynuclear compounds, such as 4:4'-amino-benzoylamino 1 hydroxybenzene -2-carboxylic acid.

Itlhas also been found that dyestuffs which behave in a quite similar manner are obtained. if the cyanuric chloride or cyanuric bromide be replaced by its heterocyclic equivalent, for example, by l-phenyl-S 5-dichlorotriazine, dichloroquinazoline, tribromcpyrimidine, 4-methyl-2z6- dichloropyrimidine, etc.

.Thus, in the free state, the new dyestuifs cor- 1 respond to the general formula in which R1 and R4 represent radicals of mononuclear compounds of the benzene series, which contain, as substituents, at least one OH-group and one COOI-I-group in the o-position to this OH-group; t represents hydrogen or an alkoxy group; R3- represents a nucleus of the benzene series, in which the NH-group and th N=N- group are placed in a position other than the o-position to each other; in which at least one 3 and at most two. y-groups represent sulphonic groups and the other y-groups hydrogen atoms,

provided that when two y-groups represent sulattach. STATES PATENT oFFlcE phonic groups they are separated by at leastone y-group representing a hydrogen atom a'nd, if the y-group' the 2-position represents a' sulphonic group, the y-group in the 4-position shall also represent a sulphonic group; and in which, finally, a: represent a connecting member or the triazine series or of another analogous heter ocyclic series.

. from a weakly alkaline dyebath in the presence Among such products those dyestufi ar par- I ticularly valuable which, in the free state, cor-,

respond to the general formula i 1 HO N'-z-i\r-R;N =N-Rl he e R1 and 3 epr n c lsa; -meeqnuclear compounds, of the henzene;se -i es whichcontain; as substituents at least one Qfi group and one CQQ-H -group the o-rpositiontg this OH-group, t represents hydrogen or v an alliogry group, R3 represents an arylene radical of the benzene series in which the NH-group and the .N=N-group are placed in p-position to each other, wherein a: and y have the meanings alone indicated.

The iollowing examples illustrate the inventioh without in any way restricting: it;

I Example 1 v 1 parts of the aminbaze compound obtained oi'H " OOH from 'diazotized i amino il-"hydroxybenzenefi-i carboxylic acid and 'leaqiiino a-rmethoxyfle rfiethylb'enzene are 'diaizotized at 157-20? '(l'in SOO pQiItS of water withzliparts lathydrbchlezic acid c? percent strength 'ahdfifid) parts' of soluhfnitrite. compound formed is filtered, and the residue on the filter' is added in a'n aqueous suspension to an aqueous solution of loltpercent of 7415 parts or the ternary condensation Zprodtfizt derived from 1 molecule of 'cyanun'c chloride, 1 molecule of 1-amino-8-hydroxynaphthalene- 3:6-disulphonicacid, 1 molecule of 4-amino-4'- h'jidro'z'ii benzene -cai hoxylic acid, and 1 molecule of aniline, to which parts "of all ammonia solution of 30 percent, stre'iig'thhasbeeii added,

and which has Been cooled with ice to o" C. The dyestufi formed is separated by means of sodium chloride after 6 hours and is dried. The product obtained has in the free state the probable formula and *is a desk-tamed pow er with eyes ect- After two 'l:idurs, 1 the 'diazoeazo;

3851' parts of the aminoazo compound obtained from diazotized 4-amino-6-sulfo-1-hydroxybenzerie-z-earteiyuc' acid andl-afifino-z-inthoiiysl-rne hyi-bee'z'ne are dia'z'otized at fie-2t o; in 5QQ'fpaYrts of with 28 parts o 'hswurb'clfibrie acid or s'o p'erc errt strength and sfs 'arts er sodium nitrite. The time eonipounarermeu'is added, afterf2 msixrsitq aquewsstiutmnt'ft 10" percent strength of 7415 parts or 'tne'ternary condensation product optameu rr'dm -1 molecule dtcvanmm chloride; 1j mci'ecule o'fl-emino-lihydioiyriaphthalene3'z'fidisulphbnic acre; 1. moieeme, of i-airiinoifhyureiiyi-liii-a benzeiie-3-foarboiylic acid, and iimolecureof-aif fie,

tdwhic'h been aaceddoparts branammorli'a The product, which in 'tliefr'ee state 11's, 9. dark! coloured powder of the probable formula --ooH dyes cotton in green shades, fast to washing,

from a weakly alkaline bath in the presence of the "hydrochloric can} termed by trze 'cbnli nsa ton marsh-green 'shaaesgrest to 'vtae'mi e;

copper sulphate and sodium tartrate.

Example 3 25.7 parts of fl aminol hydrogqr-l:1'-azobenzene-s cajrboxylic acid are added, in the form as aneu-tral solution in rooo part or water, to e fe spe sioi; of 185, tensor ermine chloride in' doo parts of water; "The l ,n emp wew r reaction mixture is kptffiit 0 14" C. 16114 hoifis,

kifingfir'eutralic'ed with the equival n awn; tit? or sea-mm carbonate. To this map-eer e of the disazo I dyestuii rep ereuty diaZbtiZd ye ae m =sc1'ro 1-myqrokyberrzehezeesrboxyiie 'ac andi animmametnbiss erature is' maimamea for 5 her-ire, the liberated l dnsatibn protect a neutrai sudden or '71.): hearts 500 parts of water with 28 parts of hydrochloric acid of 30 percent strength and 6.9 parts of sodium nitrite. The diazo-azo compound formed is added,afte1'-Q2j hours, to an aqueous solution of 10 percent' Strfength of 15.4 parts of the di-condensationlproduct obtained from 1 molecule of di-chloro-acetoguanamide, 1 molecule of l-amino- S-hydroxynaphthalene-Bz6edisulphonic acid and benzene-3-carboxylic acid, to which 50 part of an ammonia solution of 30 percent strength has been added, and which has been cooled to 0 C.

OOOH

dyes cotton in green shades, fast to light and washing, from a weakly alkaline dyebath in the presence of copper sulphate and sodium tartrate.

SOaH OCHQ Example 4 00011 Hz HOaS SOaH CH2 38.1 parts of the aminoazo compound obtained 40 from diazotized 4-amino-6-sulio-1-hydroxybenzene-2-carboxylic acid and l-amino-Z-mthoxy- 5-methylbenzene arediazotized at 1520 C. in

with ice. The dyestufi formed is salted out with sodium chloride after 6 hours and is dried.

The product, which in the free state is a darkcoloured powder of the probable formula dyes cotton in green shades, fast to washing, from a weakly alkaline dyebath in the presence of copper sulphate and sodium tartrate.

The following table gives information regarding other dyestuffs which may be prepared according to the present invention.

I II III IV V VI VII l-amino-S-hydroxyn a p h t h ale n e sulpbonic acid corresponding to the symbol H Azo dyestufl cor- Tlmd component in Component corresponding to case the component Component Component HO N res main to radical of symbol a: should 0 I ctorresdponld%g ctorresdponii%g I c o g n e e f n be a h eterocyclie g gg 0 re ice 1 o ra ice 2 compoun with 3 member I N N reactive halogenatoms ll V 1 4-amino-1-hy- 1-amino-2-methi-amino -8 -b y- Oyanuric chloride 4-amino-4-hy- 'Aniline Green.

droxy-benoxy-benzene. droxy-naphthadroxy-ll-azozene-2-carboxlens-3 :G-disnlbenzene-3-carylic acid. phonic acid. boxylic acid. I 2 4-amino-6-sulfo- 1-amino-2-methdo .do 4-amino-2-methyldo Bluish-green.

l-hydroxyoxy-5-methyl- I 4-hydroxy-] '1- b enzene-2- benzene. azobenzene-3- cagboxylic carboxylic acid. e01 3 4-amino-1-hy- 2-amino-benzoic do do 4-amino-4-hydo'. Do.

droxy-benacid. droxy-l.l-azozene-2-carboxbenzene 3 camylic acid. boxylic acid. 4 4-amino-6-su1io- 1-am1no-2-meth' do ..d0 do Methylaniline Green.

1 -h ydroxyoxy-5-methy1- benzene-2- benzene. c a r b o x yl i 0 acid. 5 do d0 d0 4-methyl-2:6-di- Bluish-green.

' chloropyrimidin) 6 do d0 do Dlichloroqninazo- D See footnote at end of table.

Example A dyebath is prepared containing 3000 parts of water, 1.5 parts of the dyestuff prepared as described in the first paragraph of Example 1 and 2 parts of anhydrous sodium carbonate. 100 parts of cotton are entered into this bath at 40-50 C., and the bath is heated during /2 hour to 90-95 0., when 30 parts of crystalline sodiumsulphate are added and dyeing is continued at thistemperature for a further hour. A solution of 100 parts of Water, 2 parts of crystalline copper sulphate and 2.5 parts of tartaric acid, which has been neutralized with caustic soda, is now added to the dyebath, and the cotton is treated for a further /z hour at about 95 (7., after which it is rinsed and dried as usual. It is dyed in a fast, pure green shade. I

The dyestuffs described in this application may also be used on composite fabrics, for example, fabrics consisting of wool and viscose staple fibre. In such cases it is advisable to dye the material in a neutral dyebath in the presence of sodium or potassium chromate.

What I claim is:

respond to the general formula i i I I IYTzNR3N=N-B4 1. The dyestuffs which, in the free state, cor'-.

wherein R1 and R4, stand for radicals of mononuclear compounds of the benzene series which contain, as substituents, at least one OH-group and one COOH-group in o-position to this OH-,

group, it stands for a member of the group consisting of hydrogen and lower alkoxy, R3 stands for an arylene radical of the benzene series in which the NI-I-group and the N=N-group are placed in a position other than the o-position to each other, wherein further at least one y and at most two ys stand for sulphonic groups and the other ys for hydrogen atoms, provided that when two ys represent sulphonic groups they are separated by at least one y representing a hydrogen atom and, if the y in the 2-position represents a sulphonic group, the y in the 4-position also represents a sulphonic group, and wherein,-

finally, :1: represents the radical of a heterocyclic;

six-membered system whose heterocyclic sixmembered ring consists of carbon and nitrogen atoms of which at least 3 and not more than in which one of the carbon valencies is linked to a radical each of the aminoazo dyestuffs, which dyestufis, in the form of their sodium salts, dis solve in water to green solutions from which the vegetable fiber is dyed green shades.

2. The dyestuffs which, in the free state, correspond to the general formula wherein R1 and R4 stand for radicals of mononuclear compounds of the benzene series which contain, as substituents, at least one OI-l-group and one COOH-group in o-position to this OH- group, R3 stands foran arylene radical of the benzeneseries' in whichthe NH-group and the N=N-group are placed in a position other than the o-position to each other, wherein further at least one y and at most two ys stand for sulphonic groups and the other ys for hydrogen atoms, provided that when two ys represent sulphonic groupsthey are separated by at least one y representing ahydrogen atom and, if the y in the 2- position represents a sulphonic group, the y in the e-position'also represents a sulphonic group,

,and wherein} finally, :0 represents the radical of a triazine complex to carbon atoms of which the' Ha HOaS wherein R1 and R4 stand. for radicals of mononuclear compounds of the benzene series which contain, as substituents, at least one OH-group and one COOH-group in o-position to this OH- group, R3 stands for an arylene radical of the' benzene series in which the NI-I-group and the N=N -g roup are placed in a position other than the o-position to each other, wherein further one 'y stands fora'sulfo-g roup and the other y for a hydrogen atom; and wherein, finally, a: represents the radical of a heterocyclic siX-membered system whose heterocyclic six-membered ring consists of carbon and nitrogen atoms of which at least 3 and not more than 4 are carbon atoms and at least 2 and not more than 3 are nitrogen atoms, not more than 2 nitrogen atoms being linked with each other, which heterocyclic sixmembered ring contains at least twice and not more than three times the atom grouping in which oneof the carbon valencies is linked to a radical each of the aminoazo dyestuffs, which dyestuffs dye cotton in green shades, fast to washing, from a weakly alkaline dyebath in the presence of copper sulfate and sodium tartrate.

4. The dyestuffs: which, inthe free-state, correspond to the generalaiormula Gil anemone wherein R1 and R4 stand for radicals of mononuclear compounds of the benzene series which contain, as substituents, at least one OH-group and one COOI-I-group in o-position to this OI-I-group, R3 stands for an arylene radical of the benzene series in which the NH-group and the -N=N-g'roup are placed in the para-position to each other, wherein further one 1 stands for a-sulfo-group and the other y for a hydrogen atom, and wherein, finally, a represents the radical of an amine selected from the group consisting of primary and secondary amines, the amine being linked to the cyanuric nucleus by a nitrogen atom, which dyestuiis dye cotton in green shades, 'fast to washing, from a weakly alkaline dyebath in the presence of copper sulfate and sodium tartrate.

6. The dyestufis which, in the free state, correspond to the general formula sulfa-group and the other for ahydrogenatom, and wherein, finally, a: represents the radical of a heterocyclic six-membered system whose heterocyclic six-membered ring consists of carbon and nitrogen atoms of which at least 3 and not more than 4 are carbon atoms and at least 2 and not more than 3 are nitrogen atoms, not more than 2 nitrogen atoms being linked with each other, which heterocyclic six-menibered ring contains at least twice and not more than three times the atom grouping in which one of the carbon valencies is linked to a. radical each of the am'inoazo dyestuffs, which dyestuffs dye cotton in green shades, fast to washing, from a weakly alkaline dyebath in the presence :of copper sulfate and sodium tartrate.

5. The dyestuffs which, inthe free state, correspond to the general formula HI H018 wherein R1 stands for the radical of a mononuclear compound of the benzene series which contains, as substituents, at least one OI-I-group and one COOI-I-group in o-position to this OH- group, wherein further one y stands for a sulfogroup and the othery for a hydrogen atom, and wherein, finally, 2 stands for the radical of an amine selected from the group consisting of primary and secondary amines, the amine being linked to the cyanuric nucleus by a nitrogen atom, which dyestufis dye cotton in green shades,

fast to washing, from a weakly alkaline dyebath in the presence of copper sulfate and sodium tartrate.

'7. The dyestufis which, in the free state, correspond to the general formula wherein R1 stands for the radical of a mononuclear compound of the benzene series which contains, as substituents, at least one OH-group and one COOK-group in o-position to this OH- group, and 2 stands for the radical of an amine selected from the group consisting of primary and secondary amines, the amine being linked to the cyanuric nucleus by a nitrogen atom,

which dyestuffs dye cotton in green shades, fast to washing, from a weakly alkaline dyebath in the presence of copper sulfate and sodium tar- 76 trate.

8. The dyestufi which, in the free state, corresponds to the formula 2: N H l I 00011 OCH; HO N(|} (ll-N N=N OH N It 0H N=N N=N C/ 0011 on: H. HOaS 9. The dyestuff which, in the free state, corresponds to the formula OTTO KAISER. 

